EP3109065B1

EP3109065B1 - Tire with tread for low temperature performance and wet traction

Info

Publication number: EP3109065B1
Application number: EP16174577.3A
Authority: EP
Inventors: Paul Harry Sandstrom; Georges Marcel Victor Thielen; Pascal Patrick Steiner; Nihat Ali Isitman
Original assignee: Goodyear Tire and Rubber Co
Current assignee: Goodyear Tire and Rubber Co
Priority date: 2015-06-24
Filing date: 2016-06-15
Publication date: 2020-04-29
Anticipated expiration: 2036-06-15
Also published as: US9650503B2; EP3109065A1; US20160376427A1

Description

Field of the Invention

This invention relates to a tire with tread for promoting a combination of winter service at low temperatures and for promoting wet traction. The tread is of or comprises a rubber composition containing low Tg styrene/butadiene elastomer and a high cis 1,4-polybutadiene rubber, along with a higher Tg liquid styrene/butadiene polymer, a traction resin and a vegetable triglyceride oil.

Background of the Invention

Tires are often desired with treads for good traction on wet surfaces. Various rubber compositions have been proposed for tire treads.
For example, tire tread rubber compositions which contain high molecular weight, high Tg (high glass transition temperature) diene based elastomer(s) might be desired for such purpose particularly for wet traction (traction of tire treads on wet road surfaces). Such tire tread may be desired where its reinforcing filler is primarily precipitated silica which may therefore be considered as being precipitated silica rich.
Such elastomers typically have a high uncured rubber viscosity (e.g. Mooney, ML1+4, viscosity) and thereby often contain a petroleum based rubber processing oil to reduce the rubber composition's uncured viscosity and to thereby promote more desirable processing conditions for the uncured rubber composition. The petroleum based rubber processing oil can be added to the elastomer prior to its addition to an internal rubber mixer (e.g. Banbury rubber mixer) or be added to the rubber mixer as a separate addition to reduce the viscosity of the rubber composition both in the internal rubber mixer and for subsequent rubber processing such as in a rubber extruder.
Here, the challenge is to reduce the cured stiffness of such tread rubber compositions, as indicated by having a lower storage modulus G' at -20°C, when the tread is intended to be used for low temperature winter conditions, particularly for vehicular snow driving.
It is considered that significant challenges are presented for providing such tire tread rubber compositions for maintaining both their wet traction while promoting low temperature (e. g. winter) performance.
To achieve such balance of tread rubber performances it is proposed to provide a tread rubber composition containing only low Tg rubbers, such as cis 1,4-polybutadiene rubber, styrene/butadiene rubber and optionally cis 1,4 polyisoprene rubber having relatively low Tg values preferably below -55°C to improve, or beneficially lower, the stiffness of the cured rubber composition at -20°C to improve winter performance in contrast to using a higher Tg SBR which would be expected to significantly increase the cured stiffness of the rubber at lower winter temperatures. To meet such challenge of providing good winter performance while maintaining wet traction for the tire tread it is also desired to use a silica-rich filler reinforcement for the tread rubber composition containing the low Tg elastomer(s) to promote wet traction combined with promoting a reduction in its cured stiffness at low temperatures, and replacing the petroleum based rubber processing oil (e. g. comprising at least one of naphthenic and paraffinic oils) with a vegetable triglyceride oil such as, for example, soybean oil to reduce its uncured rubber processing viscosity and to further reduce the Tg of the rubber composition itself to thereby promote a lower cured stiffness of the tread rubber composition at lower temperatures which will thereby positively impact and beneficially promote the low temperature winter performance of such rubber compositions. The innovation of this approach relies on the use of high Tg (comparatively higher Tg than the SBR and polybutadiene rubbers) liquid diene-based polymer (particularly a low viscosity, high Tg, styrene/butadiene polymer) and traction promoting resin in the tread rubber composition, particularly at a relatively high resin loading, to promote wet traction of the sulfur cured tread rubber which contains the vegetable triglyceride oil and only low Tg solid, particularly higher molecular weight, elastomers.
Exemplary of past soybean oil usage are US-B-7,919,553 , US-B-8,100,157 , US-B-8,022,136 and US-B-8,044,118 .
However, while vegetable oils such as soybean oil have previously been mentioned for use in various rubber compositions, including rubber compositions for tire components, use of soybean oil together with silica or precipitated silica reinforced combination of low Tg diene based elastomer(s), liquid diene based polymers and traction resin(s) for tire treads to aid in promoting a combination of both wet traction and winter tread performance is considered to be a significant departure from past practice.
In the description of this invention, the terms "compounded" rubber compositions and "compounds" are used to refer to rubber compositions which have been compounded, or blended, with appropriate rubber compounding ingredients. The terms "rubber" and "elastomer" are used interchangeably unless otherwise indicated. The amounts of materials are usually expressed in parts of material per 100 parts of rubber by weight (phr).
The glass transition temperature (Tg) of the solid elastomers and liquid polymer is determined by DSC (differential scanning calorimetry) measurements as described in ASTM D7426-08 (2013), as be understood and well known by one having skill in such art.
The number average molecular weight (Mn) of the solid elastomers and liquid polymer is determined by GPC (gel permeation chromatography) measurements as described in ASTM D5296-11, as understood and well known by one having skill in such art.
The softening point of a resin is be determined by ASTM E28 which might sometimes be referred to as a ring and ball softening point.
The term "liquid" refers to a material liquid at least at 23°C.
The term high cis 1,4-polybutadiene rubber refers to a polybutadiene rubber having a cis 1,4- isomeric content of at least 90 percent, preferably at least 95 percent.
The term low number average molecular weight liquid styrene/butadiene polymer refers to a liquid styrene/butadiene polymer having a number average molecular weight (Mn) in a range of from 1000 to 50000, preferably 3000 to 30000 or 4000 to 15000.
EP-A-2 468 815 describes a reinforced rubber composition comprising a combination of a functionalized elastomer, a liquid polymer, a filler and a resin.
EP-A-2 733 170 describes a tire rubber composition containing a combination of a resin and a vegetable oil. The vegetable oil may be a triglyceride oil and the rubber composition may comprise a functionalized elastomer and a combination of carbon black and silica as filler.

Summary and Practice of the Invention

The invention relates to a tire in accordance with claim 1.
Dependent claims refer to preferred embodiments of the invention.
In accordance with a preferred aspect of this invention, a pneumatic tire is provided having a circumferential tread intended to be ground-contacting, where said tread is or or comprises a rubber composition comprising, based on parts by weight per 100 parts by weight elastomer (phr):

(A) 100 phr of at least one diene-based elastomer comprising:
1. (1) 40 to 90 phr, alternatively 70 to 90 phr, of a styrene/butadiene elastomer having a Tg in a range of from -50°C to -85°C and preferably having an uncured Mooney viscosity (ML1+4) in a range of from 50 to 150,
2. (2) 10 to 60 phr, alternatively 10 to 30 phr, of a high cis 1,4-polybutadiene rubber having a Tg in a range of from -100°C to -105°C,
3. (3) 3 to 50 phr, alternatively 10 to 20 phr, of a low number average molecular weight liquid styrene/butadiene polymer having a Tg in a range of from -30°C to 0°C, alternatively from -25°C to -5°C, and preferably having a number average molecular weight (Mn) in a range of from 3000 to 30000 or from 4000 to 15000; and
(B) 50 to 250, alternately from 75 to 175, phr of a filler, preferably a rubber reinforcing filler, comprising a combination of silica or precipitated silica (amorphous synthetic precipitated silica) and a carbon black or a rubber reinforcing carbon black in a ratio of silica to rubber reinforcing carbon black of at least 9/1, together with a silica coupling agent having a moiety reactive with hydroxyl groups (e.g. silanol groups) on said silica or precipitated silica and another different moiety interactive with said diene-based elastomers and polymer;
(C) 5 to 45, alternatively from 7.5 to 25, phr of resin comprising at least one of terpene, coumarone indene and styrene-alphamethylstyrene resins where such resins preferably have a softening point (ASTM E28) in a range of from 60°C to 150°C; and
(D) 5 to 50, alternatively from 10 to 30 phr of a vegetable triglyceride oil.

Preferably, vegetable triglyceride oil is or comprises soybean oil.
In further accordance with this invention, the tread is provided as being sulfur cured.
Preferably, the relatively low Tg, preferably high molecular weight, styrene/butadiene elastomer has an uncured Mooney viscosity (ML1+4) in a range of from 60 to 120.
Preferably, the cis 1,4 polybutadiene rubber has a cis 1,4- isomeric content of at least 95 percent and/or an uncured Mooney viscosity (ML1+4) in a range of from 50 to 100.
In one embodiment the tread rubber composition further contains up to 25, alternately up to 15 phr or from 5 to 25 phr or from 5 to 15 phr or from 3 phr to 25 phr, of at least one additional, preferably low Tg diene based elastomer. Such additional elastomer may be or may comprise, for example, at least one of cis 1,4-polyisoprene, natural or synthetic, isoprene/butadiene and styrene/isoprene.
The styrene/butadiene elastomer may be a functionalized elastomer (e. g. end functionalized) containing at least one of siloxane, amine and thiol functional groups reactive with hydroxyl groups on said silica or precipitated silica.
The styrene/butadiene elastomer may be a tin or silicon coupled elastomer, particularly a tin coupled elastomer (e. g. coupled with the aid of tin tetrachloride).
The functionalized styrene/butadiene elastomer may be a tin or silicon coupled elastomer, particularly a tin coupled elastomer (e. g. coupled with the aid of tin tetrachloride).
The silica or the precipitated silica and the silica coupling agent may be pre-reacted to form a composite thereof prior to addition to the rubber composition.
Alternaltively, the silica or the precipitated silica and the silica coupling agent may at least partially be added to the rubber composition and least partially reacted together in situ within the rubber composition.
Preferably, the resin is be a terpene resin comprising polymers of at least one of limonene, alpha pinene and beta pinene. Preferably, it has a softening point in a range of from 60°C to 140°C.
In a preferred embodiment, the resin is a coumarone indene resin having a softening point in a range of from 60°C to 150°C.
In another preferred embodiment, the resin mis a styrene-alphamethylstyrene resin having a softening point in a range of from 60°C to 125°C, alternately from 80°C to 90°C (ASTM E28), and, preferably, a styrene content of from 10 to 30 percent.
The silica reinforcement may, for example, be characterized by having a BET surface area, as measured using nitrogen gas, in the range of, for example, 40 to 600, and more usually in a range of 50 to 300 square meters per gram. The BET method of measuring surface area is described, for example, in the Journal of the American Chemical Society, Volume 60, as well as in ASTM D3037.
The silica or precipitated silicas may, for example, also be characterized by having a dibutyl phthalate (DBP) absorption value, for example, in a range of 100 to 400, and more usually 150 to 300 cc/100g.
Various commercially available precipitated silicas may be used, such as silicas from PPG Industries under the Hi-Sil trademark with designations 210, 243 and 315, silicas from Solvay with, for example, designations of Zeosil 1165MP and Zeosil 165GR, silicas from Evonik with, for example, designations VN2 and VN3, and chemically treated precipitated silicas such as for example Agilon™ 400 from PPG.
Representative examples of rubber reinforcing carbon blacks are, for example, are referenced in The Vanderbilt Rubber Handbook, 13th edition, 1990, on Pages 417 and 418 with their ASTM designations. Such rubber reinforcing carbon blacks may have iodine absorptions ranging from, for example, 60 to 240 g/kg and DBP values ranging from 34 to 150 cc/100 g.
If desired, the vulcanizable (and vulcanized) tread rubber composition may contain an ultra high molecular weight polyethylene (UHMWPE).
Representative of silica coupling agents for the silica or precipitated silica comprise for example;

(A) bis(3-trialkoxysilylalkyl) polysulfide containing an average in range of from 1 to 5 or from 2 to 4, alternatively from 2 to 2.6 or from 3.2 to 3.8, sulfur atoms in its connecting bridge, or
(B) an organoalkoxymercaptosilane, or
(C) their combination.

Representative of such bis(3-trialkoxysilylalkyl) polysulfide is bis(3-triethoxysilylpropyl) polysulfide.
It is readily understood by those having skill in the art that the vulcanizable rubber composition would be compounded by methods generally known in the rubber compounding art. In addition said compositions could also contain fatty acid, zinc oxide, waxes, antioxidants, antiozonants and peptizing agents. As known to those skilled in the art, depending on the intended use of the sulfur vulcanizable and sulfur-vulcanized material (rubbers), the additives mentioned above are selected and commonly used in conventional amounts. Representative examples of sulfur donors include elemental sulfur (free sulfur), an amine disulfide, polymeric polysulfide and sulfur olefin adducts. Usually it is desired that the sulfur-vulcanizing agent is elemental sulfur. The sulfur-vulcanizing agent may be used in an amount ranging, for example, from 0.5 to 8 phr, with a range of from 1.5 to 6 phr being often preferred. Typical amounts of processing aids comprise 1 to 10 phr.
Additional rubber processing oils, (e. g. petroleum based rubber processing oils) may be included in the rubber composition, if desired, to aid in processing vulcanizable rubber composition in addition to the vegetable oil such as soybean oil, wherein the vegetable oil is the majority (greater than 50 weight percent or greater than 80 weight percent) of the vegetable oil and rubber processing oil.
Typical amounts of antioxidants may comprise, for example, 1 to 5 phr. Representative antioxidants may be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those disclosed in The Vanderbilt Rubber Handbook (1978), Pages 344 through 346. Typical amounts of antiozonants may comprise, for example, 1 to 5 phr. Typical amounts of fatty acids, if used, which can include stearic acid comprise 0.5 to 6 phr. Typical amounts of zinc oxide may comprise, for example, 0.5 to 5 phr. Typical amounts of waxes comprise 1 to 5 phr. Often microcrystalline waxes are used. Typical amounts of peptizers, when used, may be used in amounts of, for example, 0.1 to 1 phr. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.
Sulfur vulcanization accelerators are used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate. In one embodiment, a single accelerator system may be used, i.e., primary accelerator. The primary accelerator(s) may be used in total amounts ranging, for example, from 0.5 to 4, sometimes desirably 0.8 to 2 phr. In another embodiment, combinations of a primary and a secondary accelerator might be used with the secondary accelerator being used in amounts, such as, for example, from 0.05 to 3 phr, in order to activate and to improve the properties of the vulcanizate. Combinations of these accelerators might be expected to produce a synergistic effect on the final properties and are somewhat better than those produced by use of either accelerator alone. In addition, delayed action accelerators may be used which are not affected by normal processing temperatures but produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retarders might also be used. Suitable types of accelerators that may be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, sulfenamides, and xanthates. Often desirably the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator is often desirably a guanidine such as for example a diphenylguanidine.
The mixing of the vulcanizable rubber composition can be accomplished by methods known to those having skill in the rubber mixing art. For example, the ingredients are typically mixed in at least two stages, namely at least one non-productive stage followed by a productive mix stage. The final curatives, including sulfur-vulcanizing agents, are typically mixed in the final stage which is conventionally called the "productive" mix stage in which the mixing typically occurs at a temperature, or ultimate temperature, lower than the mix temperature(s) of the preceding non-productive mix stage(s). The rubber composition may be subjected to a thermomechanical mixing step. The thermomechanical mixing step generally comprises a mechanical working in a mixer or extruder for a period of time suitable in order to produce a rubber temperature between 140°C and 190°C. The appropriate duration of the thermomechanical working varies as a function of the operating conditions and the volume and nature of the components. For example, the thermomechanical working may be from 1 to 20 minutes.
The pneumatic tire of the present invention may be a race tire, passenger tire, aircraft tire, agricultural tire, earthmover tire, off-the-road tire or truck tire. Usually, the tire is a passenger or truck tire. The tire may also be a radial or bias ply tire, with a radial ply tire being preferred.
Vulcanization of the pneumatic tire containing the tire tread of the present invention is generally carried out at conventional temperatures in a range of, for example, from 140°C to 200°C. Often it is desired that the vulcanization is conducted at temperatures ranging from 150°C to 180°C. Any of the usual vulcanization processes may be used such as heating in a press or mold, heating with superheated steam or hot air. Such tires can be built, shaped, molded and cured by various methods which are known and will be readily apparent to those having skill in such art.
The following examples are presented for the purposes of illustrating the present invention. The parts and percentages are parts by weight, usually parts by weight per 100 parts by weight rubber (phr) unless otherwise indicated.
The liquid (low viscosity) styrene/butadiene polymer evaluated in the following Examples is identified in Table A as "styrene/butadiene A". Table A

Liquid Polymer Styrene Content Tg Number Average Molecular Weight Product

Styrene/butadiene A 25 percent -22°C 4500 Ricon™ 100¹

¹ Liquid SBR from Cray Valley

EXAMPLE I

In this example, exemplary rubber compositions for a tire tread were prepared for evaluation for use to promote wet traction and cold weather (winter) performance.
Control rubber compositions were prepared as Control rubber Sample A and Control rubber Sample B with a precipitated silica reinforced rubber composition containing styrene/butadiene rubber and cis 1,4-polybutadiene rubber together with a silica coupler for the precipitated silica reinforcement.

Experimental rubber compositions were prepared as Experimental rubber Samples C and D with soybean oil, liquid styrene/butadiene polymer and styrene-alphamethylstyrene resin being variously added to the rubber composition together with the styrene/butadiene rubber and cis 1,4-polybutadiene rubber. The rubber compositions are illustrated in the following Table 1.

Table 1

		Parts by Weight (phr)
Material	Control Sample A	Control Sample B	Exp'l Sample C	Exp'l Sample D
Styrene/butadiene rubber¹	75	75	80	85
Cis 1,4-polybutadiene rubber²	25	25	20	15
Rubber processing oil³	26	13	5	5
Soybean oil⁴	0	13	15	15
Liquid styrene/butadiene polymer A⁵	0	0	15	15
Styrene-alphamethylstyrene resin⁶	18	18	18	18
Precipitated silica⁷	140	140	140	140
Silica coupler⁸	8.1	8.1	8.1	8.1
Fatty acids⁹	5	5	5	5
Carbon black (carrier for silica coupler)	1	1	1	1
Wax	1.5	1.5	1.5	1.5
Antioxidants	3	3	3	3
Zinc oxide	2.5	2.5	2.5	2.5
Sulfur	1.2	1.4	1.4	1.4
Sulfur cure accelerators¹¹	5.5	5.7	5.7	5.7

¹A functionalized, tin coupled, styrene/butadiene rubber containing a combination of siloxy and thiol groups having a Tg of -60°C and an uncured Mooney viscosity (ML1+4) of 65 as SLR3402™ from Trinseo.
²High cis 1,4-polybutadiene rubber as BUD4001™ from The Goodyear Tire & Rubber Company having a Tg of -102°C.
³Rubber processing oil primarily comprised of naphthenic oil
⁴Soybean oil as Sterling Oil from Stratus Food Company
⁵Liquid, sulfur vulcanizable styrene/butadiene polymer having a Tg of -22°C
⁶Resin as styrene-alphamethylstyrene copolymer having a softening point in a range of 80°C to 90°C (ASTM E28) and a styrene content in a range of from 10 to 30 percent as Resin 2336™ from Eastman Chemical.
⁷Precipitated silica as Zeosil 1165MP™ from Solvay
⁸Silica coupler comprising a bis(3-triethoxysilylpropyl) polysulfide containing an average in a range of from 2 to 2.6 connecting sulfur atoms in its polysulfidic bridge as Si266 from Evonik. The coupler was a composite with carbon black as a carrier, although the coupler and carbon black are reported separately in the Table.
⁹Fatty acids comprising stearic, palmitic and oleic acids
¹⁰Sulfur cure accelerators as sulfenamide primary accelerator and diphenylguanidine secondary accelerator

The rubber Samples were prepared by identical mixing procedures, wherein the elastomers and liquid polymer with 90 phr of precipitated silica, together with silica coupler and compounding ingredients together in a first non-productive mixing stage (NP1) in an internal rubber mixer for 4 minutes to a temperature of 160°C. The resulting mixtures were was subsequently mixed in a second sequential non-productive mixing stage (NP2) in an internal rubber mixer to a temperature of 160°C with an additional 50 phr of precipitated silica. The rubber compositions were subsequently mixed in a productive mixing stage (P) in an internal rubber mixer with a sulfur cure package, namely sulfur and sulfur cure accelerator(s), for 2 minutes to a temperature of 115°C. The rubber compositions were each removed from its internal mixer after each mixing step and cooled to below 40°C between each individual non-productive mixing stage and before the final productive mixing stage.
The following Table 2 illustrates cure behavior and various physical properties of rubber compositions based upon the basic formulation of Table 1 and reported herein as Control rubber Samples A and B, and Experimental rubber Samples C and D. Where cured rubber samples are reported, such as for the stress-strain, hot rebound and hardness values, the rubber samples were cured for 14 minutes at a temperature of 160°C.
To establish the predictive wet traction, a tangent delta (tan delta) test was run at 0°C.

To establish the predictive low temperature (winter snow) performance, the cured rubber's stiffness (storage modulus G') test was run at -20°C and the rebound value at 100°C was used for predictive rolling resistance performance.

Table 2

		Parts by Weight (phr)
Materials	Control A	Control B	Exp. C	Exp. D
Styrene/butadiene rubber	75	75	80	85
Cis 1,4-polybutadiene rubber	25	25	20	15
Rubber processing oil	26	13	5	5
Soybean oil	0	13	15	15
Liquid styrene/butadiene polymer A	0	0	15	15
Styrene-alphamethylstyrene resin	18	18	18	18

Properties
Wet Traction Laboratory Prediction
Tan delta, Materials 0°C (higher is better)	0.22	0.18	0.24	0.24

Cold Weather (Winter) Performance (Stiffness) Laboratory Prediction
Storage modulus (G'), (Pa x10⁶) at -20°C, 10 Hertz, 3% strain (lower stiffness values are better)	16.6	14.7	10.6	10.9

Rolling Resistance (RR) Laboratory Prediction
Rebound at 100°C	40	40	41	41

Additional properties
Tensile strength (MPa)	8.8	8.9	9.3	8.7
Elongation at break (%)	470	580	599	611
Modulus (ring) 300 % (MPa)	5.7	4.2	4.1	3.9
Tear resistance¹ (Newtons)	49	38	36	48

¹Data obtained according to a tear strength (peal adhesion) test to determine interfacial adhesion between two samples of a rubber composition. In particular, such interfacial adhesion is determined by pulling one rubber composition away from the other at a right angle to the untorn test specimen with the two ends of the rubber compositions being pulled apart at a 180° angle to each other using an Instron instrument at 95°C and reported as Newtons force (N).

From Table 2 it is observed that:

(A) For Control rubber Sample B, 50 percent of the conventional petroleum based rubber processing oil of Control rubber Sample A was replaced with soybean oil, and the remaining composition of the sample was identical to Control rubber sample A. As a result, an improved predictive cold weather (winter) performance was obtained based on a lower storage modulus G' stiffness value of 14.7 as compared to a value of 16.6 for Control rubber Sample A. However, a loss in predictive wet traction was experienced based on a tan delta value of 0.18 compared to 0.22 for Control rubber Sample A.
(2) For Experimental rubber Samples C and D as compared to the Control, the following changes were made. The conventional rubber process oil was reduced from 26 to 5 phr, and 15 phr of soybean oil was added to the compound, along with 15 phr of the high Tg liquid SBR polymer. The only difference between samples C and D was the use of 80 phr low Tg SBR in C, along with 20 phr of PBD, and the use of 85 phr of low Tg SBR in sample D, along with 15 phr PBD. The selection of these combinations of low Tg polymers, processing oils, as conventional and soybean oil, along with the high Tg liquid SBR gave unique benefits allowing the attainment of the desired prediction of improved wet traction, tan delta values of 0.24 as compared to the control value of 0.22, and improved winter performance based on lower storage modulus G' values of 10.6 and 10.9, respectively, compared to the control value of 16.6. The results also show rebound values suggesting no loss of tire rolling resistance. This unique behavior would not be predicted without running these experiments and creating the compounds of this invention.

It is thereby concluded from Experimental rubber Samples C and D of this evaluation that a unique discovery was obtained of a sulfur cured rubber composition composed of low Tg styrene/butadiene rubber and low Tg high cis 1,4-polybutadiene rubber together with the combination of soybean oil, high Tg (comparatively higher Tg than the rubbers) liquid styrene/butadiene polymer (Tg of -22°C) and resin as shown in Experimental rubber Samples C and D, as compared to Control rubber Sample A. The desired target of improved cold weather (winter) performance (stiffness in a sense of storage modulus G' at low temperature) without a loss of predicted wet traction (in a sense of higher tan delta values at 0°C) for a tire tread performance was obtained from such a cured rubber composition.
Further, it is observed that Experimental rubber Samples C and D yielded similar hot rebound values which is predictive of maintaining a beneficially similar rolling resistance for a tire tread of these rubber compositions.

Claims

A pneumatic tire having a circumferential tread, the tread comprising a rubber composition comprising, based on parts by weight per 100 parts by weight elastomer (phr):
(A) 100 phr of at least one diene-based elastomer comprising:
(1) 40 to 90 phr of a styrene/butadiene elastomer having a Tg as measured in accordance with ASTM D 7426-08 (2013) in a range of from -50°C to - 85°C,

(2) 10 to 60 phr of a high cis 1,4-polybutadiene rubber having a Tg as measured in accordance with ASTM D 7426-08 (2013) in a range of from -100°C to - 105°C,

(3) 3 to 50 phr of a liquid styrene/butadiene polymer having a Tg as measured in accordance with ASTM D 7426-08 (2013) in a range of from -30°C to 0°C and a number average molecular weight (Mn) as measured in accordance with ASTM D 5296-11 in a range of from 1000 to 50000;

(B) 50 to 250 phr of a filler comprising a combination of silica and carbon black in a ratio of at least 9/1 together with a silica coupling agent having a moiety reactive with hydroxyl groups on said silica and another different moiety interactive with said diene-based elastomers and/or polymer;

(C) 5 to 45 phr of a resin comprising at least one of a terpene, coumarone indene and styrene-alphamethylstyrene resin; and

(D) 5 to 50 phr of a vegetable triglyceride oil.
The tire of claim 1 wherein the at least one resin or all of the resins have a softening point as measured in accordance with ASTM E28 in a range of from 60°C to 150°C.
The tire of claim 1 or 2 wherein the filler is a rubber reinforcing filler comprising a combination of precipitated silica and rubber reinforcing carbon black in a ratio of precipitated silica to rubber reinforcing carbon black of at least 9/1, together with the silica coupling agent having a moiety reactive with hydroxyl groups on said precipitated silica and another different moiety interactive with said diene-based elastomers and/or polymer.
The tire of at least one of the previous claims wherein the styrene/butadiene elastomer has an uncured Mooney viscosity (ML1+4) in a range of from 60 to 120.
The tire of at least one of the previous claims wherein the high cis 1,4-polybutadiene rubber has a cis 1,4- isomeric content of at least 95 percent and/or an uncured Mooney viscosity (ML1+4) in a range of from 50 to 100.
The tire of at least one of the previous claims wherein the rubber composition further contains up to 25 phr of at least one additional diene based elastomer comprising cis 1,4-polyisoprene having a Tg as measured in accordance with ASTM D 7426-08 (2013) below -55°C.
The tire of at least one of the previous claims wherein the styrene/butadiene elastomer is a functionalized elastomer containing at least one of siloxane, amine and thiol functional groups reactive with hydroxyl groups on the silica or the precipitated silica.
The tire of at least one of the previous claims wherein the styrene/butadiene elastomer or the functionalized styrene/butadiene elastomer is tin coupled.
The tire of at least one of the previous claims wherein the rubber composition further contains up to 25 phr or from 3 phr to 25 phr of at least one additional diene based elastomer comprising at least one of cis 1,4-polyisoprene, isoprene/butadiene, and styrene/isoprene rubber.
The tire of at least one of the previous claims wherein the silica coupling agent comprises a bis(3-triethoxysilylpropyl) polysulfide containing an average of from 1 to 5 connecting sulfur atoms in its polysulfidic bridge or comprises an alkoxyorganomercaptosilane.
The tire of at least one of the previous claims wherein the silica or the precipitated silica and the silica coupling agent are pre-reacted to form a composite thereof prior to their addition to the rubber composition; or wherein the silica or the precipitated silica and the silica coupling agent are added to the rubber composition and reacted together in situ within the rubber composition.
The tire of at least one of the previous claims wherein the resin is a terpene resin comprising polymers of at least one of limonene, alpha pinene and beta pinene and/or has a softening point as measured in accordance with ASTM E28 in a range of from 60°C to 140°C.
The tire of at least one of the previous claims wherein the resin is coumarone indene resin having a softening point as measured in accordance with ASTM E28 in a range of from 60°C to 150°C.
The tire of at least one of the previous claims wherein the resin is a styrene-alphamethylstyrene resin having a softening point as measured in accordance with ASTM E28 in a range of from 60°C to 125°C and a styrene content of from 10 to 30 percent.
The tire of at least one of the previous claims wherein the tread is sulfur cured.